JP2617620B2 - Pigment composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention is suitable for use,
It relates to an indanthrone blue pigment composition selected for its non-crystallinity and fluidity.

[0002]

BACKGROUND OF THE INVENTION Indanthrone blue pigment C.I. I. P
pigment Blue 60) is a practically useful pigment that exhibits a vivid color tone and high coloring power, and is frequently used for coloring high-molecular organic materials.

However, when dispersed in non-aqueous vehicles such as offset inks, gravure inks, and paints, it is difficult to obtain a stable dispersion, and various dispersions have a significant effect on the production work and the value of the obtained product. Aging often occurs.

[0004] For example, dispersions containing finely divided particles of I Dunthrone blue pigment often exhibit high viscosities, which during transport from the dispersing group of the product and during storage only makes it difficult to transport, or worse. In some cases, gelation occurs during storage, making it difficult to use.

[0005] When different kinds of pigments are used, color unevenness and a marked decrease in coloring power may be exhibited in a colored product due to phenomena such as color separation and sedimentation due to aggregation. Further, with respect to the surface of the coated film of the colored product, a state defect such as a decrease in gloss and a leveling defect may occur.

Further, in non-aqueous vehicles such as offset inks, gravure inks, and paints, the crystal particles of the indanthrone blue pigment, which are energetically unstable, change their size and form to shift to a stable state. The commercial value may be impaired due to a significant change in hue, a decrease in tinting strength, generation of coarse particles, and the like in the color product.

A number of proposals have been made to improve the cohesiveness and crystal stability of pigments, mainly copper phthalocyanine and quinacridone pigments.

The contents can be roughly classified into the following two when classified according to the technical method. The first law is USP33
As disclosed in US Pat. No. 70971 and US Pat. No. 2,965,511, silicon oxide, aluminum oxide and
The surface of the pigment particles is coated with a colorless compound such as tert-butylbenzoic acid.

In the second method, an organic pigment is used as a parent bone nucleus, as represented by Japanese Patent Publication No. 41-2466 and US Pat. No. 2,761,865, and a sulfon group, a sulfonamide group, an aminomethyl group, a phthalimidomethyl group, etc. This is a method of mixing compounds obtained by introducing a substituent.

The second method has a remarkable effect on the non-aggregation properties and crystal stability of the pigment in the non-aqueous vehicle as compared with the first method, and is judged from the easiness of production of the pigment composition. This is a very advantageous method.

However, there has been little research on indanthrone blue pigments.

[0012]

The present invention improves the various disadvantages of the indanthrone blue pigments described above and provides good agglomeration resistance, crystal resistance and stability to non-aqueous vehicles of a wide range of compositions. And a pigment composition that provides the fluidity of the dispersion.

[0013]

The above object is achieved by the present invention described below. That is, the pigment composition is obtained by mixing 0.3 to 30 parts by weight of the indanthrone blue pigment derivative of the formula (1) with 100 parts by weight of the indanthrone blue pigment.

[0014]

Embedded image (Wherein, R ₁ and R _2; hydrogen atom, a substituted or unsubstituted alkyl group, a nitrogen in a cycloalkyl group or R _1, R _2, may form a heterocyclic ring containing a enzyme or a sulfur atom.

R _{3 represents a} hydrogen atom or a lower alkyl group k; an integer of 1 or 2 1; an integer of 2 or 3 m; an integer of 0 or 1 n; )

There are various methods for obtaining the pigment derivative represented by the formula (1), but the following method is industrially advantageous.

That is, in polyphosphoric acid or concentrated sulfuric acid,
The compound represented by formula (2) is obtained by reacting indanthrone blue pigment with paraformaldehyde and monochloroacetic acid amide or monochloroacetic acid alkylamide, or 3-chloropropionic acid amide or its alkylamide to obtain a primary or secondary compound. This is a method of reacting a secondary amino compound.

[0018]

Embedded image (Wherein R ₃ , k and n are the same as described above).

Typical examples of the primary or secondary amine include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, isobutylamine, n-amylamine, isoamylamine, and n
-Hexylamine, octylamine, 2-ethylhexylamine, decylamine, dodecylamine, stearylamine, dimethylamine, diethylamine, di-n-butylamine, diisobutylamine, N-methylhexylamine, di-n-octylamine, di- ( 2-ethylhexyl) -amine, 2-hydroxymethylaminoethanol, diethanolamine, 3-aminopropanol,
2-aminopropanol, 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3- (2-
Ethylhexyloxy) propylamine, 3-lauryloxypropylamine, piperidine, 2-pipecholine, 4-
Pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3-piperidinemethanol, N-aminopiperidine, N-amino-4-pipecholine, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-
Methyl homopiperidine, N-methylpiperazine, 1-amino-4-cyclopentylpiperazine, 1-cyclopentylpiperazine, morpholine, thiomorpholine, dimethylaminoethylamine, ethylaminoethylamine, diethylaminoethylamine, methylaminopropylamine, dimethylaminopropylamine, diethylamino Propylamine, dibutylaminopropylamine, 2-hydroxyethylaminopropylamine, laurylaminopropylamine, diethanolaminopropylamine,
N-aminoethylpiperidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropiperidine, N-aminopropyl-2-pipecholine, N-aminopropylmorpholine and the like. .

The reaction between the compound represented by the formula (2) and the above amino compound is carried out, for example, in the presence of an excess of the amino compound at 60 to 150% in water or an inert solvent. The amino component introduced into the side chain shows strong affinity with anionic parts such as a carboxyl group of the resin component contained in the vehicle, and is considered to contribute to improving the dispersibility of the indanthrone blue pigment in various applications. .

The amount of the pigment derivative represented by the formula (1) according to the present invention in the indanthrone blue pigment is 0.3 to 3 parts by weight based on 100 parts by weight of the indanthrone blue pigment.
0 parts by weight is preferred. If the amount is less than 0.3 part by weight, the effect is reduced, and if the amount is more than 30 parts by weight, the effect of the amount used is not obtained, and there is a possibility that the various resistance of the colored material after use as a pigment composition may be deteriorated. . Most preferred is 2 to 15 parts by weight.

As a method of preparing the pigment composition, the desired effect can be sufficiently obtained by simply mixing the powder of the indanthrone blue pigment and the powder of the pigment derivative represented by the formula (1). Mechanically mix with an attritor, supermill, various pulverizers, etc., or add a solution containing the pigment derivative to a suspension system of indanthrone blue pigment with water or an organic solvent to deposit the pigment derivative on the pigment surface Or, better results can be obtained by performing a close mixing method such as co-dissolving the indanthrone blue pigment and the pigment derivative in a solvent having a strong dissolving power such as sulfuric acid and co-precipitating with a poor solvent such as water. be able to.

[0023]

The pigment composition of the present invention has a crystal transition even in an aromatic solvent at room temperature or at 160 ° C.
No growth is observed and no change in hue and tinting strength.

Further, as compared with the case where the indanthrone blue pigment is used alone, the pigment exhibits good dispersibility in the non-aqueous vehicle such as the pigment composition of the present invention or gravure ink, and has good fluidity because it does not cause aggregation. At the same time, no color separation or sedimentation of the pigment occurs even when mixed and used with different pigments.
Therefore, it is possible to obtain a beautiful colored polymer having good gloss of a printed material or a coating film.

[0025]

The synthesis of a representative compound represented by the formula (1) will be schematically described below as a production example. In the examples, parts mean parts by weight.

Production Example 1 To 150 parts of 12% fuming sulfuric acid, 10 parts of crude indanthrone blue pigment is added at 30 ° C. or less, and the mixture is stirred and dissolved. Subsequently, 9 parts of paraformaldehyde and 20 parts of manachloroacetic acid amide are added at 30 ° C. or lower, and the mixture is stirred at 25 ° C. for 50 hours, poured into ice water, filtered and washed with water, and has the following chemical structure (a). A water paste of the indanthrone blue derivative was obtained. A part was dried, analyzed for chlorine and weighed to determine the number of substituents, and found to be 1.6 per molecule.

[0027]

Embedded image The above water paste was reslurried in 200 parts of water, and 6 parts of diethylamine was added. The mixture was heated under reflux for 2 hours, filtered, washed with water,
After drying, a blue powder of an indanthrone blue derivative having the following chemical structure (b) was obtained. It is easily dissolved in dilute acetic acid and exhibits a deep blue color.

[0028]

Embedded image Production Example 2 The same reaction as in Production Example 1 was carried out except that diethylamine of Production Example 1 was replaced with 8 parts of 2-pipecholine, and the following chemical structure (c)
A blue powder of an indanthrone blue derivative having the formula was obtained. It is readily soluble in dilute acetic acid and gives a deep blue color.

[0029]

Embedded image Production Example 3 The same reaction as in Production Example 1 was carried out except that diethylamine of Production Example 1 was replaced with 8.5 parts of dimethylaminopropylamine to obtain a blue powder of an indanthrone blue derivative having the following chemical structural formula (d). . It is readily soluble in dilute acetic acid and gives a deep blue color.

[0030]

Embedded image Production Example 4 The same reaction as in Production Example 1 was carried out except that diethylamine in Production Example 1 was replaced with 8 parts of dimethylaminopropylamine to obtain a blue powder of an indanthrone blue derivative having the following chemical structure (e). It is readily soluble in dilute acetic acid and gives a deep blue color.

[0031]

Embedded image Production Example 5 To 120 parts of polyphosphoric acid heated to 80 ° C., 10 parts of crude indanthrone blue was added and dissolved, and then 4.7 parts of paraformaldehyde and 11 parts of monochloroacetamide were added. Stir for hours. Pour into warm water, filter and wash, put in 200 parts of water, add 8 parts of diethylaminoethylamine, and heat to reflux for 3 hours.
After cooling, filtration, washing with water and drying, the following chemical structure (f)
A blue powder of an indanthrone blue derivative having the formula was obtained. This is dissolved in dilute acetic acid to give a deep blue color.

[0032]

Embedded image Production Example 6 Monochloroacetic acid amide of Production Example 5 was changed to 12.6 parts of monochloroacetic acid methylamide, and the same reaction as in Production Example 5 was carried out to obtain a blue powder of an indanthrone blue derivative having the following chemical structure (g). Was. This is dissolved in dilute acetic acid to give a deep blue color.

[0033]

Embedded image Production Example 7 Monochloroacetic acid amide of Production Example 5 was changed to 12.6 parts of β-chloropropionic acid chloride, and the same reaction as in Production Example 5 was carried out. The blue color of an indanthrone blue derivative having the following chemical structure (h) was obtained. A powder was obtained. This is dissolved in dilute acetic acid to give a deep blue color.

[0034]

Embedded image Hereinafter, an example and a comparative example will be described.

The chemical structure of each compound indicated by the alphabet corresponds to that shown in Production Examples.

Examples 1 to 9 An alkyd melamine resin varnish for baking paint was prepared by using the indanthrone blue pigment of the formula (1) alone (comparative example) and the indanthrone blue pigment each of the compounds shown in Production Examples 1 to 7 The mixed pigment composition of the present invention was blended so that the pigment content was 6% by weight, and dispersed by a ball mill to prepare a paint. Table 1 shows the measurement results having the viscosity immediately after removal and storage for one month.

The alkyd melamine paint using the pigment composition according to Example 1 was excellent in fluidity and crystal stability, and was excellent in hue beautifulness, coloring power, and glossiness in a coating film. I was Furthermore, the storage stability was excellent with little change in viscosity.

[0038]

[Table 1] The dispersion stability will be compared with the examples of color-coding stability which is particularly problematic in use.

The paint shown in the examples of Table 1 was cut with a base paint of cut titanium oxide prepared in advance with an alkyd melamine resin varnish so that the ratio of pigment to titanium oxide became 1/10, and a light-colored paint was obtained. obtain.

The light-colored paint was further diluted with xylene, adjusted with a Four Cup No. 4 for 20 seconds (25 ° C.), poured into a test tube, and observed for changes in the glass wall surface.

[0041]

Table 2 shows the paint of Example 1 as an example, but the paints of Examples 2 to 9 show the same behavior as that of Example 1 and show that the pigment composition according to the present invention has excellent results. Was.

Examples 10 to 16 Ingredients obtained by mixing a gravure vinyl chloride varnish with the indanthrone blue pigment of the formula (1) alone (comparative example) and the indanthrone blue pigment with the compounds shown in Production Examples 1 to 7 The inventive pigment composition was blended so that the pigment content was 10% by weight, and dispersed by a bead mill to prepare a gravure ink. The results of examining the viscosity are shown in Table 3, and those according to the present invention are excellent in fluidity. Excellent results were also obtained with respect to the effects on the clarity, transparency, coloring and gloss of the color tone of the printed matter printed with the gravure ink.

[0043]

Example 17 A rosin-modified phenolic resin-based offset ink varnish was prepared by adding the indanthrone blue pigment of the formula (1) alone (comparative example) and the compound (f) to the indanthrone blue pigment in a ratio of 90:10. The offset ink was adjusted so that the pigment content of each of the mixed pigment compositions became 20%, and the fluidity of the inks was compared with a parallel plate viscometer. The results of the present invention showed remarkably excellent results.

In the printed matter, the results of the present invention were selected in terms of color tone clarity, coloring power, transparency and gloss.

[Table 2]

[Table 2]

Claims (1)

(57) [Claims] An indanthrone blue pigment derivative of the formula (1) is added to 100 parts by weight of indanthrone blue pigment.
A pigment composition obtained by mixing up to 30 parts by weight. Embedded image (Wherein, R ₁ and R _2;. Hydrogen atom, a substituted or unsubstituted alkyl group, a nitrogen in a cycloalkyl group or R _1, R _2, may form a heterocyclic ring containing a enzyme or a sulfur atom R ₃ A hydrogen atom or a lower alkyl group k; an integer of 1 or 2; an integer of 2 or 3 m; an integer of 0 or 1 n; an integer of 1 to 4.)